JP2007182489A - Flame-retardant glass fiber-reinforced resin composition - Google Patents
Flame-retardant glass fiber-reinforced resin composition Download PDFInfo
- Publication number
- JP2007182489A JP2007182489A JP2006001104A JP2006001104A JP2007182489A JP 2007182489 A JP2007182489 A JP 2007182489A JP 2006001104 A JP2006001104 A JP 2006001104A JP 2006001104 A JP2006001104 A JP 2006001104A JP 2007182489 A JP2007182489 A JP 2007182489A
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- glass fiber
- resin composition
- metal salt
- reinforced resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000003063 flame retardant Substances 0.000 title claims abstract description 137
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000011521 glass Substances 0.000 title claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 99
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 42
- -1 alkali metal salt Chemical class 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 16
- 229920005668 polycarbonate resin Polymers 0.000 claims description 16
- 239000004431 polycarbonate resin Substances 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 18
- 238000002485 combustion reaction Methods 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
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- 238000011156 evaluation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229960001755 resorcinol Drugs 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
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- 229910052708 sodium Inorganic materials 0.000 description 5
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- 229920006361 Polyflon Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
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- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
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- 238000004381 surface treatment Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- JDWGPDRDUUNFIB-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,5-undecafluoropentane-2-sulfonic acid Chemical compound OS(=O)(=O)C(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JDWGPDRDUUNFIB-UHFFFAOYSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- 239000000956 alloy Substances 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
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- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
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- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
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- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- ZQOXGRIKWKXDIJ-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZQOXGRIKWKXDIJ-UHFFFAOYSA-M 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
Description
本発明は難燃性ガラス繊維強化樹脂組成物に関し、更に詳しくは、表面に難燃剤が付着したガラス繊維と熱可塑性樹脂からなり、機械的強度、寸法安定性、溶融熱安定性、成形性に優れた難燃性ガラス繊維強化樹脂組成物に関する。 The present invention relates to a flame retardant glass fiber reinforced resin composition. More specifically, the present invention comprises a glass fiber having a flame retardant attached to a surface and a thermoplastic resin, and has mechanical strength, dimensional stability, heat stability, and moldability. The present invention relates to an excellent flame retardant glass fiber reinforced resin composition.
熱可塑性樹脂は、成形加工の容易さ、外観、経済性、機械的強度、その他、物理的、化学的特性に優れているため、電気・電子・ＯＡ機器、精密機械、自動車部品、建材、雑貨等の幅広い分野で使用されている。このように熱可塑性樹脂の使用分野が拡大するにつれ、樹脂成形品の薄肉化も進み、更に強度、剛性、寸法安定性に優れた材料が求められている。このため、ガラス繊維を配合した熱可塑性樹脂組成物が広く用いられている。
一方、近年、電気・電子・ＯＡ機器等の用途を中心に、使用する熱可塑性樹脂の難燃化の要望が強く、これらの要望に応えるために多数の難燃剤が開発検討されている。熱可塑性樹脂の難燃化には主にハロゲン化合物が使用され、多くの場合、さらに三酸化アンチモン等が難燃助剤として併用されてきた。難燃剤としてハロゲン系化合物を熱可塑性樹脂に配合した場合には、難燃化の効果は比較的大きいが、火災発生時あるいは焼却処理時に環境汚染を引き起こす恐れがあり、また機械的性質を損なったり、成形時の変色、さらに高温で長期に使用した場合の物性低下や着色したりするなどの問題を有している。このため使用されるハロゲン系化合物の減量化が望まれている。
Thermoplastic resins have excellent physical and chemical properties, such as ease of molding, appearance, economy, mechanical strength, etc., so electrical, electronic and OA equipment, precision machinery, automotive parts, building materials, miscellaneous goods It is used in a wide range of fields. Thus, as the field of use of thermoplastic resins expands, the thickness of resin molded products has also been reduced, and materials having superior strength, rigidity, and dimensional stability are being demanded. For this reason, thermoplastic resin compositions containing glass fibers are widely used.
On the other hand, in recent years, there has been a strong demand for flame retardancy of thermoplastic resins to be used mainly in applications such as electrical / electronic / OA equipment, and many flame retardants have been developed and studied in order to meet these demands. Halogen compounds are mainly used for flame retardancy of thermoplastic resins, and in many cases, antimony trioxide or the like has also been used in combination as a flame retardant aid. When a halogen-based compound is blended with a thermoplastic resin as a flame retardant, the flame retardant effect is relatively great, but there is a risk of causing environmental pollution in the event of a fire or incineration, and the mechanical properties may be impaired. Further, there are problems such as discoloration at the time of molding and deterioration of physical properties and coloring when used for a long time at high temperature. For this reason, reduction of the halogen-type compound used is desired.
ハロゲン系化合物の減量化を目的として、芳香族オリゴマー系リン酸エステルが使用されるが、優れた難燃性を得るためには、芳香族オリゴマー系リン酸エステルを多量に添加する必要があり、そのため機械的性質や熱的性質が損なわれるという欠点があった。 Aromatic oligomeric phosphate esters are used for the purpose of reducing the amount of halogenated compounds, but in order to obtain excellent flame retardancy, it is necessary to add a large amount of aromatic oligomeric phosphate ester, For this reason, there is a drawback that mechanical properties and thermal properties are impaired.
特にガラス繊維強化熱可塑性樹脂組成物の非ハロゲン系難燃剤による難燃化の方法としては、芳香族オリゴマー系リン酸エステルの他にも、例えばポリカーボネート樹脂にガラス繊維およびメラミン・シアヌル酸付加物を配合してなる難燃性ガラス繊維強化樹脂組成物が開示されている（特許文献１）。しかし、非強化樹脂組成物に比べて、熱可塑性樹脂をガラス繊維で強化したガラス繊維強化樹脂組成物の場合、ガラス繊維が芯の作用をして燃焼しやすくなる蝋燭効果により、特許文献１も含め、ガラス繊維強化樹脂組成物の場合、非強化樹脂組成物と同じ難燃剤の使用量では、難燃性が不足し、かつ難燃性のバラツキも大きく、実用性に乏しかった。
また、芳香族ポリカーボネート１００重量部、芳香族ポリカーボネートを除く熱可塑性樹脂０〜４０重量部、ガラス繊維等無機化合物粒子０．０１〜１重量部、アルカリ金属塩およびアルカリ土類金属塩から選ばれる少なくとも１種の金属塩０．０００１〜１重量部、フルオロポリマーからなる難燃性樹脂組成物も開示されている（特許文献２）が、特許文献２のガラス繊維の配合された難燃性樹脂組成物の場合も、上記蝋燭効果により難燃性が不足し、かつ難燃性のバラツキも大きく、機械的強度や寸法安定性の改良も不十分であった。
In particular, as a method of flame-retarding a glass fiber reinforced thermoplastic resin composition with a non-halogen flame retardant, glass fiber and a melamine / cyanuric acid adduct are added to, for example, a polycarbonate resin in addition to an aromatic oligomeric phosphate ester. A flame retardant glass fiber reinforced resin composition is disclosed (Patent Document 1). However, in the case of a glass fiber reinforced resin composition in which a thermoplastic resin is reinforced with glass fiber as compared with a non-reinforced resin composition, Patent Document 1 also has a candle effect that the glass fiber acts as a core and easily burns. In addition, in the case of the glass fiber reinforced resin composition, with the same amount of flame retardant used as in the non-reinforced resin composition, the flame retardancy was insufficient, the flame retardant variation was large, and the practicality was poor.
Also, at least selected from 100 parts by weight of an aromatic polycarbonate, 0 to 40 parts by weight of a thermoplastic resin excluding the aromatic polycarbonate, 0.01 to 1 part by weight of inorganic compound particles such as glass fiber, an alkali metal salt and an alkaline earth metal salt A flame retardant resin composition comprising 0.0001 to 1 part by weight of one metal salt and a fluoropolymer is also disclosed (Patent Document 2), but the flame retardant resin composition containing the glass fiber of Patent Document 2 is disclosed. In the case of a product, flame retardance was insufficient due to the above-mentioned candle effect, flame retardant variation was large, and mechanical strength and dimensional stability were not improved sufficiently.
以上のように、従来技術で得られる難燃性ガラス繊維強化樹脂組成物は、多量に配合される難燃剤及び難燃助剤に起因する（１）環境汚染、（２）溶融熱安定性不足による変色、成形性や機械的強度の低下、（３）高温あるいは高湿度雰囲気で長期に使用した場合の変色や機械的強度低下の問題等があり、実用性の乏しいものであった。
本発明の目的は、従来技術の諸問題を解決し、難燃剤の配合が少量であることにより環境負荷が小さく、溶融熱安定性、成形性、寸法安定性、剛性に優れ、薄肉での難燃性にも優れたガラス繊維強化樹脂組成物及びその成形品を提供することにある。 The object of the present invention is to solve the problems of the prior art, and because the amount of the flame retardant is small, the environmental load is small, the heat stability, the moldability, the dimensional stability and the rigidity are excellent, and it is difficult to make it thin. The object is to provide a glass fiber reinforced resin composition having excellent flammability and a molded product thereof.
本発明者は、上記課題を達成するために鋭意検討した結果、表面に微量の難燃剤が付着したガラス繊維を熱可塑性樹脂に配合することより、環境負荷が小さく、極めて優れた難燃性を有するだけでなく、ガラス繊維強化樹脂組成物が本来有する外観、溶融熱安定性、成形性、寸法安定性、剛性等をも同時に維持された、優れた難燃性ガラス繊維強化樹脂組成物及びその成形品となることを見出し、本発明を完成させた。
すなわち本発明の要旨は、熱可塑性樹脂（Ａ）１００重量部に対し、表面に難燃剤（Ｃ−１）が付着してなるガラス繊維（Ｂ）を１〜１００重量部配合してなる難燃性ガラス繊維強化樹脂組成物、及びこれを成形してなる難燃性ガラス繊維強化樹脂成形品にある。
As a result of intensive studies to achieve the above-mentioned problems, the present inventor has less environmental impact and extremely excellent flame retardancy than by blending glass fibers having a small amount of flame retardant attached on the surface thereof into a thermoplastic resin. In addition to having the appearance, melting heat stability, moldability, dimensional stability, rigidity, etc. originally possessed by the glass fiber reinforced resin composition, an excellent flame retardant glass fiber reinforced resin composition and its As a result, the present invention was completed.
That is, the gist of the present invention is that flame retardant is obtained by blending 1 to 100 parts by weight of glass fiber (B) having a flame retardant (C-1) attached to the surface with respect to 100 parts by weight of thermoplastic resin (A). The glass fiber reinforced resin composition and the flame retardant glass fiber reinforced resin molded product formed by molding the same.
本発明の難燃性ガラス繊維強化樹脂組成物、及び難燃性ガラス繊維強化樹脂成形品は、ガラス繊維表面に難燃剤を付着させることにより、いわゆるガラス繊維の蝋燭効果による樹脂の燃焼性が著しく抑制されているので、難燃剤の使用量が極めて少なくても安定した難燃効果があり、環境負荷が小さく、ガラス繊維強化樹脂組成物が本来有する外観、溶融熱安定性、成形性、寸法安定性、剛性等も同時に維持されており、電気・電子・ＯＡ機器、精密機械、自動車部品、建材、雑貨をはじめ幅広い用途へ使用することが期待できる。 The flame retardant glass fiber reinforced resin composition and the flame retardant glass fiber reinforced resin molded product of the present invention have a remarkable flame retardant property of the resin due to the so-called glass fiber candle effect by attaching a flame retardant to the glass fiber surface. Because it is suppressed, there is a stable flame retardant effect even if the amount of flame retardant used is extremely small, the environmental impact is small, the appearance inherent in glass fiber reinforced resin composition, melt heat stability, moldability, dimensional stability The properties, rigidity, etc. are maintained at the same time, and it can be expected to be used for a wide range of applications including electrical / electronic / OA equipment, precision machinery, automotive parts, building materials, general goods.
以下、本発明について具体的に説明する。
本発明においては、熱可塑性樹脂（Ａ）と、表面に難燃剤（Ｃ−１）が付着してなるガラス繊維（Ｂ）から成る樹脂組成物において、更に難燃剤（Ｃ−２）、及び含フッ素樹脂（Ｄ）を配合して、より高い難燃性を付与した樹脂組成物とするのが好ましい。
本発明に使用される熱可塑性樹脂（Ａ）は、特に限定されず、例えば芳香族ポリカーボネート樹脂；ポリエチレン樹脂、ポリプロピレン樹脂等のオレフィン系樹脂；ポリスチレン樹脂、ＡＳ樹脂、ＡＢＳ樹脂、ＡＥＳ樹脂等のスチレン系樹脂；ＰＭＭＡ樹脂等のメタクリル系樹脂；ポリオキシメチレン（ポリアセタール）樹脂；ポリアミド６、ポリアミド６６、ポリアミドＭＸＤ等のポリアミド系樹脂；変性ポリフェニレンエーテル（ＰＰＥ）系樹脂；ポリフェニレンサルファイド樹脂；ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂等のポリエステル系樹脂；液晶ポリマー等の熱可塑性樹脂、又は、これらの熱可塑性樹脂の少なくとも２種類以上の樹脂から成るポリマーアロイを挙げることができる。中でも、芳香族ポリカーボネート樹脂、ポリアミド系樹脂、変性ポリフェニレンエーテル系樹脂、ポリエステル系樹脂、及び芳香族ポリカーボネート樹脂／ポリエステル系樹脂、芳香族ポリカーボネート樹脂／スチレン系樹脂のポリマーアロイ樹脂組成物から構成された群から選択された熱可塑性樹脂を使用することが好ましく、芳香族ポリカーボネート樹脂が特に好ましい。
Hereinafter, the present invention will be specifically described.
In the present invention, in the resin composition comprising the thermoplastic resin (A) and the glass fiber (B) formed by attaching the flame retardant (C-1) to the surface, the flame retardant (C-2) and It is preferable to blend a fluororesin (D) to obtain a resin composition having higher flame retardancy.
The thermoplastic resin (A) used in the present invention is not particularly limited. For example, aromatic polycarbonate resin; olefin resin such as polyethylene resin and polypropylene resin; styrene such as polystyrene resin, AS resin, ABS resin, and AES resin. Methacrylic resin such as PMMA resin; polyoxymethylene (polyacetal) resin; polyamide resin such as polyamide 6, polyamide 66, polyamide MXD; modified polyphenylene ether (PPE) resin; polyphenylene sulfide resin; polyethylene terephthalate (PET) ) Resins, polyester resins such as polybutylene terephthalate (PBT) resins; thermoplastic resins such as liquid crystal polymers, or polymer alloys composed of at least two of these thermoplastic resins. That. Among them, groups composed of aromatic polycarbonate resins, polyamide resins, modified polyphenylene ether resins, polyester resins, and aromatic polycarbonate resins / polyester resins, aromatic polycarbonate resins / styrene resin polymer alloy resin compositions It is preferable to use a thermoplastic resin selected from the group consisting of aromatic polycarbonate resins.
本発明に使用される芳香族ポリカーボネート樹脂は、芳香族ヒドロキシ化合物またはこれと少量のポリヒドロキシ化合物をホスゲンまたは炭酸のジエステルと反応させることによって得られる分岐していてもよい熱可塑性芳香族ポリカーボネート重合体または共重合体である。本発明に使用されるポリカーボネート樹脂の製造方法は任意であり、従来公知のホスゲン法（界面重合法）や、溶融法（エステル交換法）等により製造したものを使用することが出来る。さらに、溶融法を用いた場合には、末端基のＯＨ基量を調整した芳香族ポリカーボネート樹脂を使用することができる。 The aromatic polycarbonate resin used in the present invention is an optionally branched thermoplastic aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound or a small amount thereof with a diester of phosgene or carbonic acid. Or a copolymer. The production method of the polycarbonate resin used in the present invention is arbitrary, and those produced by a conventionally known phosgene method (interfacial polymerization method), a melting method (transesterification method) or the like can be used. Furthermore, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups of terminal groups is adjusted can be used.
原料の芳香族ジヒドロキシ化合物としては、２，２−ビス（４−ヒドロキシフェニル）プロパン（＝ビスフェノールＡ）、テトラメチルビスフェノールＡ、ビス（４−ヒドロキシフェニル）−ｐ−ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、４，４−ジヒドロキシジフェニルなどが挙げられ、好ましくはビスフェノールＡである。また、本発明の目的である難燃性をさらに高める目的で上記の芳香族ジヒドロキシ化合物にスルホン酸テトラアルキルホスホニウムが１個以上結合した化合物を使用することもできる。 As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound may be used for the purpose of further improving the flame retardancy, which is the object of the present invention.
分岐した芳香族ポリカーボネート樹脂を得るには、フロログルシン、４，６−ジメチル−２，４，６−トリス（４−ヒドロキシフェニル）ヘプテン−２、４，６−ジメチル−２，４，６−トリス（４−ヒドロキシフェニル）ヘプタン、２，６−ジメチル−２，４，６−トリス（４−ヒドロキシフェニル）ヘプテン−３、１，３，５−トリス（４−ヒドロキシフェニル）ベンゼン、１，１，１−トリス（４−ヒドロキシフェニル）エタンなどで示されるポリヒドロキシ化合物、あるいは３，３−ビス（４−ヒドロキシアリール）オキシインドール（＝イサチンビスフェノール）、５−クロルイサチン、５，７−ジクロルイサチン、５−臭素イサチンなどを前記芳香族ジヒドロキシ化合物の一部として用いればよく、使用量は、０．０１〜１０モル％であり、好ましくは０．１〜２モル％である。 In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 A polyhydroxy compound represented by tris (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5- Bromine isatin or the like may be used as part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol. A%, preferably 0.1 to 2 mol%.
芳香族ポリカーボネート樹脂の分子量を調節するには、一価芳香族ヒドロキシ化合物を用いればよく、ｍ−又はｐ−メチルフェノール、ｍ−又はｐ−プロピルフェノール、ｐ−ｔ−ブチルフェノール及びｐ−長鎖アルキル置換フェノールなどが挙げられる。 In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. M- or p-methylphenol, m- or p-propylphenol, pt-butylphenol and p-long chain alkyl Examples thereof include substituted phenols.
本発明に使用される芳香族ポリカーボネート樹脂は、好ましくは、２，２−ビス（４−ヒドロキシフェニル）プロパンから誘導される芳香族ポリカーボネート樹脂、または２，２−ビス（４−ヒドロキシフェニル）プロパンと他の芳香族ジヒドロキシ化合物とから誘導される芳香族ポリカーボネート共重合体が挙げられる。 The aromatic polycarbonate resin used in the present invention is preferably an aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane And aromatic polycarbonate copolymers derived from other aromatic dihydroxy compounds.
本発明に使用される芳香族ポリカーボネート樹脂の分子量は適宜選択して決定すればよいが、一般的には溶媒としてメチレンクロライドを用い、温度２５℃で測定された溶液粘度より換算した粘度平均分子量が１４，０００〜３２，０００であることが好ましく、中でも１７，０００〜２３，００であることが好ましい。 The molecular weight of the aromatic polycarbonate resin used in the present invention may be appropriately selected and determined, but in general, methylene chloride is used as a solvent, and the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. It is preferably 14,000 to 32,000, and more preferably 17,000 to 23,000.
本発明に使用されるガラス繊維（Ｂ）は特に制限はなく、例えばＥガラス、Ｃガラス、Ａガラス、Ｓガラス等のガラス繊維を挙げることができる。これらの中で、アルカリ分が少なく、電気的特性が良好なＥガラスの繊維を特に好適に用いることができる。ガラス繊維（Ｂ）の平均繊維径は特に制限されないが、例えば１〜１００μｍの範囲で選ぶことが好ましく、より好ましくは２〜５０μｍ、更に好ましくは３〜３０μｍ、特に好ましくは５〜２０μｍである。平均繊維径が１μｍ未満のガラス繊維 は、製造が容易でなく、コスト高になる恐れがあり、一方１００μｍを超えると、ガラス繊維の引張強度が低下する恐れがある。ガラス繊維（Ｂ）の平均繊維長は特に限定されないが、例えば０．１〜２０ｍｍの範囲で選ぶことが好ましく、０．３〜５ｍｍであることがより好ましい。ガラス繊維（Ｂ）の平均繊維長が０．１ｍｍ未満であると、補強効果が十分に発現しない恐れがあり、２０ｍｍを超えると、得られる熱可塑性樹脂組成物の成形が困難になる恐れがある。
又、ガラス繊維と共にミルドファイバーあるいはガラスフレーク等を添加して成形品の異方性を改良することも可能で、その場合はミルドファイバー及びガラスフレークも同様に難燃剤で表面処理するとガラス繊維の場合と同様に、難燃性の向上効果があり、より好ましい。
There is no restriction | limiting in particular in the glass fiber (B) used for this invention, For example, glass fibers, such as E glass, C glass, A glass, and S glass, can be mentioned. Among these, fibers of E glass having a low alkali content and good electrical characteristics can be particularly preferably used. The average fiber diameter of the glass fiber (B) is not particularly limited, but is preferably selected in the range of, for example, 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. Glass fibers having an average fiber diameter of less than 1 μm are not easy to manufacture and may increase costs, while if it exceeds 100 μm, the tensile strength of the glass fibers may decrease. Although the average fiber length of glass fiber (B) is not specifically limited, For example, it is preferable to select in the range of 0.1-20 mm, and it is more preferable that it is 0.3-5 mm. If the average fiber length of the glass fiber (B) is less than 0.1 mm, the reinforcing effect may not be sufficiently exhibited, and if it exceeds 20 mm, molding of the resulting thermoplastic resin composition may be difficult. .
It is also possible to improve the anisotropy of the molded product by adding milled fiber or glass flake together with the glass fiber. In that case, if the surface of the milled fiber and glass flake is treated with a flame retardant, it is the case of glass fiber. Like the above, there is an effect of improving flame retardancy, which is more preferable.
ガラス繊維（Ｂ）表面に難燃剤（Ｃ−１）を付着させる方法は、ガラス繊維の表面処理法、すなわち、浸漬塗布、ローラ塗布、吹き付け塗布、流し塗布、スプレー塗布などの公知の方法を任意に用いることができる。例えば、カップリング剤、潤滑剤、帯電防止剤、ＰＨ調整剤、水など、通常用いられる配合剤と同様に難燃剤（Ｃ−１）を集束剤に配合し、該集束剤を用いて上記表面処理法によりガラス繊維（Ｂ）の表面に難燃剤（Ｃ−１）を付着させることができる。 As a method of attaching the flame retardant (C-1) to the surface of the glass fiber (B), any known method such as dip coating, roller coating, spray coating, flow coating, spray coating or the like can be used. Can be used. For example, a flame retardant (C-1) is blended in a sizing agent in the same manner as a commonly used compounding agent such as a coupling agent, a lubricant, an antistatic agent, a pH adjusting agent, and water, and the surface is formed using the sizing agent. A flame retardant (C-1) can be made to adhere to the surface of glass fiber (B) by a processing method.
ガラス繊維（Ｂ）の集束剤としては特に制限はなく、例えば、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体、アクリル樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂などの樹脂エマルジョン等を挙げることができ、好ましくはアクリル樹脂、エポキシ樹脂、ポリウレタン樹脂である。
またカップリング剤としては、例えば、ビニルトリクロロシラン、メチルビニルジクロロシラン等のクロロシラン系化合物、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等のアルコキシシラン系化合物、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン等のエポキシシラン系化合物や、アクリル系化合物、イソシアネート系化合物、チタネート系化合物、エポキシ系化合物などを挙げることができる。
There is no restriction | limiting in particular as a sizing agent of glass fiber (B), For example, resin emulsions, such as a vinyl acetate resin, an ethylene-vinyl acetate copolymer, an acrylic resin, an epoxy resin, a polyurethane resin, a polyester resin, etc. can be mentioned. Preferably, acrylic resin, epoxy resin, and polyurethane resin are used.
Examples of the coupling agent include chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropyltrimethoxysilane. Compounds, epoxy silane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, acrylic compounds, isocyanate compounds, titanate compounds, epoxy compounds And so on.
ガラス繊維（Ｂ）表面に付着させる難燃剤（Ｃ−１）、又はそれとは別に樹脂組成物中に配合される難燃剤（Ｃ−２）は特に制限されず、ハロゲン系難燃剤、リン酸エステル系難燃剤、金属塩系難燃剤、シリコーン系難燃剤などが例示される。難燃剤（Ｃ−１）としては、例えば金属塩系難燃剤（Ｅ）、シリコーン系難燃剤（Ｆ）を挙げることができ、好ましくは金属塩系難燃剤（Ｅ）である。 The flame retardant (C-1) attached to the surface of the glass fiber (B) or the flame retardant (C-2) blended in the resin composition separately is not particularly limited, and is a halogen-based flame retardant or phosphate ester. Examples thereof include a flame retardant, a metal salt flame retardant, and a silicone flame retardant. Examples of the flame retardant (C-1) include a metal salt flame retardant (E) and a silicone flame retardant (F), preferably a metal salt flame retardant (E).
該金属塩系難燃剤（Ｅ）としては、含フッ素アルカンスルホン酸金属塩（Ｈ）又は芳香族スルホン酸金属塩（Ｉ）であり、より好ましくは含フッ素アルカンスルホン酸金属塩（Ｈ）はパーフルオロアルカンスルホン酸金属塩（Ｊ）であり、芳香族スルホン酸金属塩（Ｉ）は置換基として炭素数３〜３０の分岐炭化水素基を有する置換芳香族スルホン酸金属塩（Ｋ）であり、さらに含フッ素アルカンスルホン酸金属塩（Ｈ）、芳香族スルホン酸金属塩（Ｉ）及び置換芳香族スルホン酸金属塩（Ｋ）の金属が、アルカリ金属又はアルカリ土類金属であるのが好ましい。該アルカリ金属及びアルカリ土類金属としては、具体的にはナトリウム、リチウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウム等が挙げられ、好ましくは、ナトリウム、カリウム、セシウムである。 The metal salt flame retardant (E) is a fluorine-containing alkanesulfonic acid metal salt (H) or an aromatic sulfonic acid metal salt (I), more preferably a fluorine-containing alkanesulfonic acid metal salt (H). It is a fluoroalkanesulfonic acid metal salt (J), and the aromatic sulfonic acid metal salt (I) is a substituted aromatic sulfonic acid metal salt (K) having a branched hydrocarbon group having 3 to 30 carbon atoms as a substituent. Further, the metal of the fluorine-containing alkanesulfonic acid metal salt (H), the aromatic sulfonic acid metal salt (I) and the substituted aromatic sulfonic acid metal salt (K) is preferably an alkali metal or an alkaline earth metal. Specific examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, and sodium, potassium, and cesium are preferable.
本発明の含フッ素アルカンスルホン酸金属塩（Ｈ）中で、最も好ましく使用されるパーフルオロアルカン−スルホン酸金属塩（Ｊ）の具体例としては、パーフルオロブタン−スルホン酸ナトリウム、パーフルオロブタン−スルホン酸カリウム、パーフルオロメチルブタン−スルホン酸ナトリウム、パーフルオロメチルブタン−スルホン酸カリウム、パーフルオロオクタン−スルホン酸ナトリウム、パーフルオロオクタン−スルホン酸カリウムなどが挙げられる。 Specific examples of the perfluoroalkane-sulfonic acid metal salt (J) most preferably used in the fluorine-containing alkanesulfonic acid metal salt (H) of the present invention include perfluorobutane-sodium sulfonate, perfluorobutane- Examples thereof include potassium sulfonate, sodium perfluoromethylbutane-sulfonate, potassium perfluoromethylbutane-sulfonate, sodium perfluorooctane-sulfonate, potassium perfluorooctane-sulfonate.
本発明の芳香族スルホン酸金属塩（Ｉ）中で、最も好ましく使用される、炭素数３〜３０の分岐炭化水素基を置換基として有する置換芳香族スルホン酸金属塩（Ｋ）の分岐炭化水素基の具体例として、ｉ−プロピル基、ｓｅｃ−ブチル基、ｔ−ブチル基、イソペンチル基、イソヘキシル基、イソヘプチル基、イソオクチル基、イソノニル基、イソデシル基、イソウンデシル基、イソドデシル基、イソトリデシル基、イソテトラデシル基、イソペンタデシル基、イソヘキサデシル基、イソヘプタデシル基、イソオクタデシル基、イソノナデシル基、イソエイコシル基、プロピレンの４量体等の、分岐アルキル基であることが好ましい。芳香族スルホン酸金属塩（Ｉ）は、複数の分岐炭化水素基を置換基として有していても良い。中でも難燃効果付与の観点から、この分岐炭化水素基が炭素数３以上３０以下で、且つ全置換基の炭素数の合計（全置換基の総炭素数）が６以上６０以下、中でも１２以上４０以下であることが好ましい。 The branched hydrocarbon of the substituted aromatic sulfonic acid metal salt (K) having a branched hydrocarbon group having 3 to 30 carbon atoms as a substituent, which is most preferably used in the aromatic sulfonic acid metal salt (I) of the present invention. Specific examples of the group include i-propyl group, sec-butyl group, t-butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group, isododecyl group, isotridecyl group, isotetradecyl group A branched alkyl group such as a tetramer of decyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group, isoeicosyl group or propylene is preferable. The aromatic sulfonic acid metal salt (I) may have a plurality of branched hydrocarbon groups as substituents. Among these, from the viewpoint of imparting a flame retardant effect, this branched hydrocarbon group has 3 to 30 carbon atoms, and the total number of carbon atoms of all substituents (total carbon number of all substituents) is 6 to 60, especially 12 or more. It is preferable that it is 40 or less.
置換芳香族スルホン酸金属塩（Ｋ）としては、中でも本発明の樹脂組成物や樹脂成形品における難燃性と入手の容易さからドデシルベンゼンスルホン酸ナトリウム塩、ドデシルベンゼンスルホン酸カリウム塩、ドデシルベンゼンスルホン酸セシウム塩から選択される１種以上であるであることが好ましい。 As the substituted aromatic sulfonic acid metal salt (K), dodecylbenzenesulfonic acid sodium salt, dodecylbenzenesulfonic acid potassium salt, dodecylbenzene, among others, from the flame retardancy and availability of the resin composition and resin molded product of the present invention. One or more selected from cesium sulfonates are preferred.
また、該金属塩系難燃剤は、２種以上を混合して使用してもよい。中でも本発明の樹脂組成物や樹脂成形品における難燃性の観点から、アルカリ金属塩であることが好ましく、特にナトリウム、カリウム、セシウムのいずれかの塩であることが好ましい。 Moreover, you may use this metal salt type flame retardant in mixture of 2 or more types. Among these, from the viewpoint of flame retardancy in the resin composition and resin molded product of the present invention, an alkali metal salt is preferable, and a salt of sodium, potassium, or cesium is particularly preferable.
本発明に使用されるシリコーン系難燃剤（Ｆ）としては、シリコーン系難燃剤（Ｆ）の付着したガラス繊維（Ｂ）を熱可塑性樹脂（Ａ）に添加した場合、熱可塑性樹脂（Ａ）の難燃性を改良することができる種々のシリコーン、或いはシリコーン含有化合物が含まれる。具体的には、シリカ粉末の表面にポリオルガノシロキサンを担持させた粉末状シリコーン（ｆ−１）、主鎖が分岐構造を有し、珪素に結合する芳香族基を有する分岐シリコーン化合物（ｆ−２）、芳香族基含有環状ポリオルガノシロキサン及び直鎖状ポリオルガノシロキサンを含有するシリコーン化合物（ｆ−３）、ポリオルガノシロキサン粒子の存在下に、ビニル系重合体を重合して得られるポリオルガノシロキサン（ｆ−４）等が好ましく使用される。 As the silicone flame retardant (F) used in the present invention, when the glass fiber (B) to which the silicone flame retardant (F) is attached is added to the thermoplastic resin (A), the thermoplastic flame retardant (A) Various silicones or silicone-containing compounds that can improve flame retardancy are included. Specifically, a powdery silicone (f-1) having a polyorganosiloxane supported on the surface of a silica powder, a branched silicone compound having a branched structure in the main chain and an aromatic group bonded to silicon (f- 2) A polyorganopolymer obtained by polymerizing a vinyl polymer in the presence of an aromatic group-containing cyclic polyorganosiloxane and a linear polyorganosiloxane-containing silicone compound (f-3) and polyorganosiloxane particles Siloxane (f-4) and the like are preferably used.
このシリカ粉末の表面にポリオルガノシロキサンを担持させた粉末状シリコーン（ｆ−１）としては、例えば、東レ・ダウコーニング社より商品名：トレフィルＦ２０２として市販されている。また、主鎖が分岐構造を有し、珪素に結合する芳香族基を有する分岐シリコーン化合物（ｆ−２）は、特開平１１−１４０２９４号公報、特開平１０−１３９９６４号公報及び特開平１１−２１７４９４号公報等に記載の方法で製造され、例えば、信越化学工業（株）から商品名：Ｘ−４０−９８０５等、一部は市販されており、容易に入手することができる。芳香族基含有環状ポリオルガノシロキサン及び直鎖状ポリオルガノシロキサンを含有するシリコーン化合物（ｆ−３）は、特開２００２−５３７４６号公報に記載されるように、公知の方法で製造することができる。 The powdery silicone (f-1) in which polyorganosiloxane is supported on the surface of the silica powder is commercially available, for example, as Toray Fill F202 from Toray Dow Corning. Further, branched silicone compounds (f-2) having a branched structure in the main chain and an aromatic group bonded to silicon are disclosed in JP-A-11-140294, JP-A-10-139964, and JP-A-11-11. It is manufactured by the method described in No. 217494, etc., for example, a part name such as trade name: X-40-9805 from Shin-Etsu Chemical Co., Ltd. is commercially available and can be easily obtained. The silicone compound (f-3) containing an aromatic group-containing cyclic polyorganosiloxane and a linear polyorganosiloxane can be produced by a known method as described in JP-A-2002-53746. .
また、ポリオルガノシロキサン粒子の存在下に、ビニル系重合体を重合して得られるポリオルガノシロキサン（ｆ−４）は、ＷＯ０３−４５０６明細書あるいはＷＯ０３−９１３４２明細書等に記載の方法で製造され、ポリオルガノシロキサン粒子は平均粒子径０．０８〜０．６μｍの粒子のものが好ましく使用される。例えば、このポリオルガノシロキサン粒子４０〜９０重量％の存在下にビニル系重合体を６０〜１０重量％重合して得られる。また、このようなポリオルガノシロキサン（ｆ−４）は、（株）カネカより商品名：カネエースＸＳ等として市販されており、容易に入手できるものが使用可能である。 A polyorganosiloxane (f-4) obtained by polymerizing a vinyl polymer in the presence of polyorganosiloxane particles is produced by the method described in WO03-4506, WO03-91342, or the like. Polyorganosiloxane particles having an average particle diameter of 0.08 to 0.6 μm are preferably used. For example, it can be obtained by polymerizing 60 to 10% by weight of a vinyl polymer in the presence of 40 to 90% by weight of the polyorganosiloxane particles. Such polyorganosiloxane (f-4) is commercially available from Kaneka Co., Ltd. under the trade name: Kane Ace XS, and can be easily obtained.
本発明でガラス繊維（Ｂ）の表面に付着させる難燃剤（Ｃ−１）としては、好ましくは上記の金属塩系難燃剤（Ｅ）又はシリコーン系難燃剤（Ｆ）であり、より好ましくは金属塩系難燃剤（Ｅ）であるが、これらとは別に樹脂組成物中に難燃剤（Ｃ−２）を配合する場合には、これら金属塩系難燃剤（Ｅ）及びシリコーン系難燃剤（Ｆ）の他に、リン酸エステル系難燃剤も好ましく用いられる。 In the present invention, the flame retardant (C-1) to be adhered to the surface of the glass fiber (B) is preferably the metal salt flame retardant (E) or the silicone flame retardant (F), more preferably a metal. Although it is a salt flame retardant (E), when the flame retardant (C-2) is blended in the resin composition separately from these, these metal salt flame retardant (E) and silicone flame retardant (F In addition, a phosphate ester flame retardant is also preferably used.
本発明に使用されるリン酸エステル系難燃剤（Ｇ）としては、好ましくは、下記の一般式（１）または（２）で表されるリン酸エステル系化合物が挙げられる。 The phosphate ester flame retardant (G) used in the present invention is preferably a phosphate ester compound represented by the following general formula (1) or (2).
（式中、Ｒ１、Ｒ2およびＲ３は、それぞれ、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｈ、ｉおよびｊは、それぞれ０または１を示す。）。 (Wherein R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, h, i and j Each represents 0 or 1).
（式中、Ｒ4、Ｒ5、Ｒ6およびＲ7は、それぞれ、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｐ、ｑ、ｒおよびｓは、それぞれ０または１であり、ｍは１から５の数であり、Ｘはアリーレン基を示す）。 (Wherein R 4 , R 5 , R 6 and R 7 each represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, p, q, r and s are each 0 or 1, m is a number from 1 to 5, and X represents an arylene group).
上記一般式（１）で表されるリン酸エステル系化合物としては、例えば、リン酸トリフェニル、リン酸トリクレジル、リン酸ジフェニル−２−エチルクレジル、リン酸トリ（イソプロピルフェニル）、メチルホスホン酸ジフェニルエステル、フェニルホスホン酸ジエチルエステル、リン酸ジフェニルクレジル、リン酸トリブチル等が挙げられる。一般式（１）で表されるリン系化合物は、公知の方法で、オキシ塩化リン等から製造することができる。 Examples of the phosphate ester compound represented by the general formula (1) include triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, Examples include phenylphosphonic acid diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate. The phosphorus compound represented by the general formula (1) can be produced from phosphorus oxychloride or the like by a known method.
上記一般式（２）で表されるリン酸エステル系化合物としては、ｍが１〜５の縮合リン酸エステルであり、ｍが単一の縮合リン酸エステルであってもよく、あるいはｍが異なる縮合リン酸エステルの混合物であってもよい。混合物である場合は、混合物のｍの平均値が１〜５であればよい。Ｘはアリーレン基を示し、例えばレゾルシノール、ハイドロキノン、ビスフェノールＡ等のジヒドロキシ化合物から誘導される基である。一般式（２）で表されるリン酸エステル系化合物としては、例えば、ジヒドロキシ化合物がレゾルシノールである場合は、フェニルレゾルシノール・ポリホスフェート、クレジル・レゾルシノール・ポリホスフェート、フェニル・クレジル・レゾルシノール・ポリホスフェート、キシリル・レゾルシノール・ポリホスフェート、フェニル−ｐ−ｔ−ブチルフェニル・レゾルシノール・ポリホスフェート、フェニル・イソプロピルフェニル・レゾルシノール・ポリホスフェート、クレジル・キシリル・レゾルシノール・ポリホスフェート、フェニル・イソプロピルフェニル・ジイソプロピルフェニル・レゾルシノール・ポリホスフェート等が挙げられる。 As the phosphate ester compound represented by the general formula (2), m is a condensed phosphate ester of 1 to 5, m may be a single condensed phosphate ester, or m is different. It may be a mixture of condensed phosphate esters. When it is a mixture, the average value of m of the mixture may be 1 to 5. X represents an arylene group, for example, a group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A or the like. Examples of the phosphoric ester compound represented by the general formula (2) include, when the dihydroxy compound is resorcinol, phenyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl cresyl resorcinol polyphosphate, Xylyl-resorcinol-polyphosphate, phenyl-pt-butylphenyl-resorcinol-polyphosphate, phenyl-isopropylphenyl-resorcinol-polyphosphate, cresyl-xylyl-resorcinol-polyphosphate, phenyl-isopropylphenyl-diisopropylphenyl-resorcinol- Examples include polyphosphate.
本発明におけるガラス繊維（Ｂ）の表面に付着する難燃剤（Ｃ−１）の量は、難燃剤（Ｃ−１）の付着したガラス繊維（Ｂ）を熱可塑性樹脂（Ａ）に添加した場合、熱可塑性樹脂（Ａ）の難燃性を改良することができる量であれば特に制限されない。この目安としては、樹脂組成物に難燃剤（Ｃ−２）を添加しなくても、ＵＬ−９４規格で厚み１．６ｍｍの垂直燃焼試験の結果がＶ−２以上となることである。
例えば、本発明においては、難燃剤（Ｃ−１）として金属塩系難燃剤（Ｅ）を用いる場合、０．００１〜５ｗｔ％であるガラス繊維（Ｂ）を用いることが好ましく、０．００５〜１ｗｔ％であるガラス繊維（Ｂ）を用いることが特に好ましい。該金属塩系難燃剤（Ｅ）の付着量が０．００１ｗｔ％未満では、難燃性ガラス繊維強化樹脂組成物の難燃性が不足し、５ｗｔ％を越えると樹脂組成物の熱安定性が低下するので好ましくない。
The amount of the flame retardant (C-1) attached to the surface of the glass fiber (B) in the present invention is the case where the glass fiber (B) attached with the flame retardant (C-1) is added to the thermoplastic resin (A). If it is the quantity which can improve the flame retardance of a thermoplastic resin (A), it will not restrict | limit in particular. As a guideline, even if the flame retardant (C-2) is not added to the resin composition, the result of the vertical combustion test with a thickness of 1.6 mm according to the UL-94 standard is V-2 or more.
For example, in this invention, when using a metal salt type flame retardant (E) as a flame retardant (C-1), it is preferable to use the glass fiber (B) which is 0.001-5 wt%, and 0.005- It is particularly preferable to use 1 wt% glass fiber (B). When the adhesion amount of the metal salt flame retardant (E) is less than 0.001 wt%, the flame retardancy of the flame retardant glass fiber reinforced resin composition is insufficient, and when it exceeds 5 wt%, the thermal stability of the resin composition is low. Since it falls, it is not preferable.
本発明において、このような表面に難燃剤（Ｃ−１）を付着させたガラス繊維の使用量としては、熱可塑性樹脂１００重量部に対して１〜１００重量部であることが必要であり、好ましくは５〜８０重量部である。
また、本発明においては、強化剤のガラス繊維としては、上述したような表面に難燃剤（Ｃ−１）を付着させたガラス繊維（Ｂ）を使用することが必要であり、全量が該ガラス繊維（Ｂ）であるのが良いが、一部を該ガラス繊維（Ｂ）以外のガラス繊維を使用したものであっても良い。
In the present invention, the amount of the glass fiber having the flame retardant (C-1) attached to such a surface needs to be 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin, Preferably it is 5-80 weight part.
Moreover, in this invention, it is necessary to use the glass fiber (B) which made the flame retardant (C-1) adhere to the surface as mentioned above as glass fiber of a reinforcing agent, and the whole quantity is this glass. The fiber (B) may be used, but a part of the glass fiber (B) other than the glass fiber (B) may be used.
更に本発明において、難燃剤（Ｃ−２）を使用する場合の配合量としては、ガラス繊維（Ｂ）の表面に付着した難燃剤（Ｃ−１）では所望の難燃性を満足することが困難な場合に難燃性を補うために配合するのであり、表面に難燃剤を付着させないガラス繊維を用いた場合よりも、（Ｃ−１）、（Ｃ−２）の合計よりも少ない量で所望の難燃性を達成することができる。その量は目的の難燃性の程度や難燃剤の種類にもよるが、例えば熱可塑性樹脂１００重量部に対し、金属塩系難燃剤（Ｅ）の場合、０．００１〜１．０重量部の範囲であり、シリコーン系難燃剤（Ｆ）の場合、０．１〜１０重量部の範囲であり、リン酸エステル系難燃剤（Ｇ）の場合、１〜２０重量部の範囲である。 Furthermore, in this invention, as a compounding quantity when using a flame retardant (C-2), the flame retardant (C-1) adhering to the surface of glass fiber (B) may satisfy desired flame retardance. When it is difficult, it is blended to compensate for flame retardancy, and in a smaller amount than the sum of (C-1) and (C-2), compared to the case of using glass fibers that do not attach a flame retardant to the surface. Desired flame retardancy can be achieved. The amount depends on the intended degree of flame retardancy and the type of flame retardant, but for example, 0.001 to 1.0 part by weight in the case of the metal salt flame retardant (E) with respect to 100 parts by weight of the thermoplastic resin. In the case of the silicone flame retardant (F), it is in the range of 0.1 to 10 parts by weight, and in the case of the phosphate ester flame retardant (G), it is in the range of 1 to 20 parts by weight.
本発明の難燃性ガラス繊維強化樹脂組成物には、更に含フッ素樹脂（Ｄ）を配合することが好ましく、含フッ素樹脂（Ｄ）としては、従来公知のものを使用できる。例えばフルオロオレフィン樹脂等が挙げられる。フルオロオレフィン樹脂としては、通常フルオロエチレン構造を含む重合体あるいは共重合体である。具体的にはジフルオロエチレン樹脂、テトラフルオロエチレン樹脂、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合樹脂等が挙げられる。好ましくはテトラフルオロエチレン樹脂等が挙げられる。このフルオロエチレン樹脂としては、フィブリル形成能を有するフルオロエチレン樹脂が挙げられる。 The flame-retardant glass fiber reinforced resin composition of the present invention preferably further contains a fluorine-containing resin (D), and a conventionally known one can be used as the fluorine-containing resin (D). For example, fluoroolefin resin etc. are mentioned. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Preferably tetrafluoroethylene resin etc. are mentioned. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.
本発明に使用される、フィブリル形成能を有するフルオロエチレン樹脂としては、例えば三井・デュポンフロロケミカル社製の商品名：テフロン（登録商標）６Ｊ、ダイキン化学工業社製の商品名：ポリフロンＦ２０１Ｌ、ポリフロンＦ１０３、さらにフルオロエチレン樹脂の水性分散液の市販品として、三井デュポンフロロケミカル社製の商品名：テフロン（登録商標）３０Ｊ、ダイキン化学工業社製の商品名：フルオンＤ−１等が挙げられ、これらを使用することができる。また本発明においては、ビニル系単量体を重合してなる多層構造を有するフルオロエチレン重合体も使用することができ、具体的には三菱レイヨン社製の商品名：メタブレンＡ−３８００等が挙げられる。 Examples of the fluoroethylene resin having fibril-forming ability used in the present invention include trade names: Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., trade names: Polyflon F201L, Polyflon manufactured by Daikin Chemical Industries, Ltd. As commercial products of F103, and further an aqueous dispersion of fluoroethylene resin, trade name: Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., trade name: Fullon D-1 manufactured by Daikin Chemical Industries, etc. These can be used. In the present invention, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used, and specifically, trade name: Metabrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd. and the like can be mentioned. It is done.
本発明における含フッ素樹脂（Ｄ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して０．１〜３重量部である。含フッ素樹脂（Ｂ）の含有量が少なすぎると、得られる難燃性ガラス繊維強化樹脂組成物の難燃性が不十分となり、逆に多すぎても難燃性ガラス繊維強化樹脂成形品の外観不良や機械的強度の低下が生ずる場合がある。よって本発明における含フッ素樹脂（Ｄ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して、好ましくは０．１〜２重量部である。 Content of the fluororesin (D) in this invention is 0.1-3 weight part with respect to 100 weight part of thermoplastic resins (A). When there is too little content of a fluorine-containing resin (B), the flame retardance of the flame-retardant glass fiber reinforced resin composition obtained will become inadequate, and conversely, too much flame-retardant glass fiber reinforced resin molded article Appearance defects and mechanical strength reduction may occur. Therefore, the content of the fluororesin (D) in the present invention is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
本発明の難燃性ガラス繊維強化樹脂組成物には、上記成分以外に、必要に応じて、本発明の効果を損なわない範囲で、従来公知の任意の難燃剤、紫外線吸収剤、亜リン酸エステルやリン酸エステル等のリン系熱安定剤、フェノール系抗酸化剤、衝撃改良剤、蛍光増白剤、酸化チタン等の着色剤、滑剤、カーボン繊維、シリカ・アルミナ繊維、ジルコニア繊維、ホウ素繊維、窒化ホウ素繊維、窒化ケイ素チタン酸カリウム繊維、金属繊維等の無機繊維、シリカ、マイカ、タルク等の無機充填材、離型剤、摺動性改良剤等の添加剤を含有していてもよい。 In the flame-retardant glass fiber reinforced resin composition of the present invention, in addition to the above components, if necessary, any conventionally known flame retardant, ultraviolet absorber, phosphorous acid, as long as the effects of the present invention are not impaired. Phosphorous heat stabilizers such as esters and phosphate esters, phenolic antioxidants, impact modifiers, fluorescent brighteners, colorants such as titanium oxide, lubricants, carbon fibers, silica / alumina fibers, zirconia fibers, boron fibers Inorganic fibers such as boron nitride fiber, silicon nitride potassium titanate fiber and metal fiber, inorganic fillers such as silica, mica and talc, additives such as mold release agent and slidability improver may be contained. .
本発明の難燃性ガラス繊維強化樹脂組成物の製造方法は、特に制限されるものではなく、例えば、熱可塑性樹脂（Ａ）、表面に難燃剤（Ｃ−１）が付着したガラス繊維（Ｂ）、さらに必要により配合される難燃剤（Ｃ−２）、含フッ素樹脂（Ｄ）、紫外線吸収剤、リン系熱安定剤、フェノール系抗酸化剤、酸化チタン等の着色剤等を一括溶融混練する方法や、熱可塑性樹脂（Ａ）、さらに必要により配合される難燃剤（Ｃ−１）、含フッ素樹脂（Ｄ）、紫外線吸収剤、リン系熱安定剤、フェノール系抗酸化剤、酸化チタン等の着色剤を予め混合後、表面に難燃剤（Ｃ−１）が付着したガラス繊維（Ｂ）を溶融混練する方法などが挙げられる。 The method for producing the flame retardant glass fiber reinforced resin composition of the present invention is not particularly limited. For example, a thermoplastic resin (A), a glass fiber (B-1) having a flame retardant (C-1) attached to the surface thereof (B ), And flame retardant (C-2), fluorine-containing resin (D), ultraviolet absorber, phosphorus heat stabilizer, phenolic antioxidant, titanium oxide and other colorants, etc., which are blended as necessary. Method, thermoplastic resin (A), flame retardant (C-1), fluorine-containing resin (D), ultraviolet absorber, phosphorus thermal stabilizer, phenolic antioxidant, titanium oxide And a method of melt-kneading the glass fiber (B) having the flame retardant (C-1) attached to the surface thereof.
各成分を混合し溶融混練する方法としては、従来公知の任意の、ガラス繊維強化熱可塑性樹脂組成物に適用される方法を適用することができる。具体的には例えば、リボンブレンダー、ヘンシェルミキサー、バンバリーミキサー、ドラムタンブラー、単軸または二軸スクリュー押出機、コニーダーなどを使用する方法等が挙げられる。溶融混練温度は熱可塑性樹脂の種類とガラス繊維の配合率に応じて適宜選択して決定すればよいが、通常２００〜３５０℃の範囲である。 As a method of mixing and melt-kneading each component, any conventionally known method applied to a glass fiber reinforced thermoplastic resin composition can be applied. Specific examples include a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single or twin screw extruder, a kneader, and the like. The melt kneading temperature may be appropriately selected and determined according to the type of thermoplastic resin and the blending ratio of glass fibers, but is usually in the range of 200 to 350 ° C.
本発明の難燃性ガラス繊維強化樹脂成形品は、上述してきた、本発明の難燃性ガラス繊維強化熱可塑性樹脂組成物を、従来公知の任意の各種成形方法にて成形し、得ることができる。成形方法としては、熱可塑性樹脂の成形に適用できる方法をそのまま適用することができ、射出成形法、押出成形法、中空成形法、回転成形法、圧縮成形法、差圧成形法、トランスファー成形法などが挙げられる。 The flame retardant glass fiber reinforced resin molded product of the present invention can be obtained by molding the flame retardant glass fiber reinforced thermoplastic resin composition of the present invention as described above by any of various known molding methods. it can. As a molding method, a method applicable to the molding of a thermoplastic resin can be applied as it is, an injection molding method, an extrusion molding method, a hollow molding method, a rotational molding method, a compression molding method, a differential pressure molding method, a transfer molding method. Etc.
本発明の難燃性ガラス繊維強化樹脂成形品は、ガラス繊維表面に難燃剤を付着させることにより、いわゆるガラス繊維の蝋燭効果による樹脂の燃焼性が著しく抑制されているので、難燃剤の使用量が極めて少なくても安定した難燃効果があり、環境負荷が小さく、ガラス繊維強化樹脂組成物が本来有する外観、溶融熱安定性、成形性、寸法安定性、剛性等をも同時に維持されており、電気・電子・ＯＡ機器、精密機械、自動車部品、建材、雑貨をはじめ幅広い用途へ使用することが期待できる。 In the flame-retardant glass fiber reinforced resin molded product of the present invention, the flame retardant is adhered to the glass fiber surface, so that the flammability of the resin due to the so-called glass fiber candle effect is remarkably suppressed. Even if there is very little, it has a stable flame retardant effect, has a small environmental load, and maintains the original appearance, melting heat stability, moldability, dimensional stability, rigidity, etc. inherent to the glass fiber reinforced resin composition. It can be expected to be used for a wide range of applications including electrical / electronic / OA equipment, precision machinery, automobile parts, building materials, and miscellaneous goods.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はその要旨を越えない限り、以下の例に限定されるものではない。
（熱可塑性樹脂）
ポリカーボネート樹脂：ポリ４，４−イソプロピリデンジフェニルカーボネート 商品名：ユーピロン（登録商標）Ｓ−３０００ 粘度平均分子量２１０００ （三菱エンジニアリングプラスチックス（株）製品）
（ガラス繊維）
ＧＦ−１：日本電気硝子（株）製 Ｔ−５７１と同様のガラス繊維の表面処理処方で、分岐化ドデシルベンゼンスルホン酸ナトリウム塩を配合して製造して得られた表面に分岐化ドデシルベンゼンスルホン酸ナトリウム塩を０．２ｗｔ％（付着量）付着してなるガラス繊維
ＧＦ−２：日本電気硝子（株）製 Ｔ−５７１と同様のガラス繊維の表面処理処方で、分岐化ドデシルベンゼンスルホン酸ナトリウム塩を配合して製造して得られた表面に分岐化ドデシルベンゼンスルホン酸ナトリウム塩を１．０ｗｔ％（付着量）付着してなるガラス繊維
ＧＦ−３：日本電気硝子（株）製 商品名：Ｔ−５７１
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following examples, unless the summary is exceeded.
(Thermoplastic resin)
Polycarbonate resin: Poly 4,4-isopropylidene diphenyl carbonate Product name: Iupilon (registered trademark) S-3000 Viscosity average molecular weight 21000 (Mitsubishi Engineering Plastics Co., Ltd. product)
(Glass fiber)
GF-1: A surface treatment prescription of glass fiber similar to T-571 manufactured by Nippon Electric Glass Co., Ltd. Branched dodecylbenzenesulfone on the surface obtained by blending with sodium dodecylbenzenesulfonate sodium salt Glass fiber formed by attaching 0.2 wt% (adhesion amount) of sodium acid salt GF-2: Surface treatment prescription of glass fiber similar to T-571 manufactured by Nippon Electric Glass Co., Ltd. Branched sodium dodecylbenzenesulfonate Glass fiber formed by adhering 1.0 wt% (adhesion amount) of branched dodecylbenzenesulfonic acid sodium salt to the surface obtained by blending salt GF-3: manufactured by Nippon Electric Glass Co., Ltd. T-571
（難燃剤）
難燃剤−１：パーフルオロブタンスルホン酸カリウム塩（ＫＦＢＳ） 三菱マテリアル（株）製
難燃剤−２：分岐化ドデシルベンゼンスルホン酸カリウム塩
難燃剤−３：シリコーン系コアシェル難燃剤 商品名：カネエースＸＳ （株）カネカ製
難燃剤−４：レゾルシンジキシリルホスフェート 商品名：ＰＸ−２００ 大八化学（株）製
（含フッ素樹脂）
ＰＴＦＥ：フィブリル形成性ポリテトラフルオロエチレン樹脂 商品名：ポリフロンＦ２０１Ｌ ダイキン工業（株）製
(Flame retardants)
Flame Retardant-1: Perfluorobutanesulfonic acid potassium salt (KFBS) Made by Mitsubishi Materials Corporation Flame retardant-2: Branched dodecylbenzenesulfonic acid potassium salt Flame retardant-3: Silicone core shell flame retardant Product name: Kane Ace XS ( Kaneka Corp. Flame Retardant-4: Resorcin Dixyl Phosphate Product Name: PX-200 Made by Daihachi Chemical Co., Ltd. (fluorinated resin)
PTFE: fibril forming polytetrafluoroethylene resin Product name: Polyflon F201L manufactured by Daikin Industries, Ltd.
（評価方法）
燃焼性： ＵＬ−９４規格に準拠し、１．６ｍｍ厚みの燃焼試験片にて垂直燃焼試験を実施した。
曲げ弾性率： ＡＳＴＭ Ｄ−７９０に従って測定した。
熱安定性比較試験：コンパウンド後のペレットの分子量と、通常成形品（サイクル時間４０秒）で成形された５０ｍｍ角、３ｍｍ厚の平板の分子量を測定し、それらの分子量変化を確認した。
(Evaluation methods)
Combustibility: In accordance with UL-94 standard, a vertical combustion test was performed using a 1.6 mm-thickness combustion specimen.
Flexural modulus: measured according to ASTM D-790.
Thermal stability comparison test: The molecular weight of the pellet after compounding and the molecular weight of a 50 mm square and 3 mm thick flat plate molded with a normal molded product (cycle time 40 seconds) were measured, and changes in the molecular weight were confirmed.
実施例１
ＰＣ１００重量部に対して、ＧＦ−１を１１．１重量部、ＰＴＦＥを０．１１重量部添加しタンブラーにて１５分ブレンドを行い、その後、単軸押出機にて３００℃のシリンダー温度にて押し出しペレット化した。
そのペレットを用い、射出成形機にて２８０℃のシリンダー温度、８０℃の金型温度にて燃焼試験片および曲げ試験片を成形した。
尚、５０ｍｍ角、３ｍｍ厚の平板については、４０秒サイクルで試験片の成形を実施した。
以上を用い、上記の通り評価した結果を表１に示す。
Example 1
11.1 part by weight of GF-1 and 0.11 part by weight of PTFE are added to 100 parts by weight of PC, blended for 15 minutes with a tumbler, and then at a cylinder temperature of 300 ° C. with a single screw extruder. Extruded pelletized.
Using the pellets, a combustion test piece and a bending test piece were molded by an injection molding machine at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
In addition, about the flat plate of 50 mm square and 3 mm thickness, shaping | molding of the test piece was implemented in the 40 second cycle.
The results evaluated as described above are shown in Table 1.
実施例２〜７
実施例１と同様の方法にて、表１に示す組成にてサンプルの作成、及び評価を実施した。その評価結果を表１に示す。
Examples 2-7
Samples were prepared and evaluated with the compositions shown in Table 1 in the same manner as in Example 1. The evaluation results are shown in Table 1.
比較例１〜５
実施例１と同様の方法にて、表２に示す組成にてサンプルの作成、及び評価を実施した。その評価結果を表２に示す。
Comparative Examples 1-5
Samples were prepared and evaluated with the compositions shown in Table 2 in the same manner as in Example 1. The evaluation results are shown in Table 2.
表１及び表２から、通常のガラス繊維を使用した組成物では、比較例−１に示す様に総燃焼時間も２０８秒と長く、最大燃焼時間も７３秒と長くて、燃焼性の評価がＶ−２ＮＧであるのに対して、実施例―１では、難燃剤付着ガラス繊維を使用することで、総燃焼時間も１２０秒、最大燃焼時間が２７秒と短縮され、燃焼性もＶ−２評価となり、燃焼性が大幅に改善された。
さらに、実施例−２では、更にこの難燃剤付着ガラス繊維の他に難燃剤を添加することにより、燃焼性の評価もＶ−０であり、しかも総燃焼時間も２４秒、最大燃焼時間も４秒と短く、Ｖ−０に対して余裕が認められる。一方、通常のガラス繊維を使用し、組成物中に難燃剤を添加した比較例−２及び比較例−３では、いずれも燃焼性の評価はＶ−０になったが、最大燃焼時間は９秒と１０秒であり、余裕をもったＶ−０評価ではない。特に、比較例−２では、実施例−２に合わせて、ＧＦ−１に使用している難燃剤をその添加により組成物中に含有される量に相当する量を別途添加しており、組成物中に存在する難燃剤量としては、実施例−２と比較例−２とはほぼ同量であるが、上記のように、明らかに実施例−２の方が難燃性の改善効果が見受けられた。
更に、実施例−３や実施例−７では難燃剤付着ガラス繊維量を増やした場合においても、優れた難燃性が安定して得られた。
From Table 1 and Table 2, in the composition using normal glass fiber, as shown in Comparative Example-1, the total combustion time is as long as 208 seconds, the maximum combustion time is as long as 73 seconds, and the combustibility is evaluated. In contrast to V-2NG, in Example-1, the use of the flame retardant-attached glass fiber shortens the total combustion time to 120 seconds, the maximum combustion time to 27 seconds, and the flammability is also V-2. As a result, the flammability was greatly improved.
Furthermore, in Example-2, by adding a flame retardant in addition to this flame retardant-attached glass fiber, the evaluation of flammability is also V-0, and the total combustion time is 24 seconds, and the maximum combustion time is 4 It is as short as 2 seconds, and a margin is recognized for V-0. On the other hand, in Comparative Example-2 and Comparative Example-3 in which normal glass fiber was used and a flame retardant was added to the composition, the evaluation of combustibility was V-0, but the maximum combustion time was 9 Second and 10 seconds, not a V-0 evaluation with a margin. In particular, in Comparative Example-2, in addition to Example-2, an amount corresponding to the amount contained in the composition by adding the flame retardant used in GF-1 was added separately, and the composition As the amount of the flame retardant present in the product, Example-2 and Comparative Example-2 are almost the same amount, but as described above, Example-2 clearly has an effect of improving flame retardancy. It was seen.
Further, in Example-3 and Example-7, excellent flame retardancy was stably obtained even when the amount of the flame retardant-attached glass fiber was increased.
また、実施例−５では別に添加する難燃剤を分岐化ドデシルベンゼンスルホン酸カリウム塩に変更したが、同じ難燃剤を使用し、難燃剤量もガラス繊維に付着させた量の相当量を含めて添加した比較例−３と比べても、優れた難燃性を示している。
実施例−６では、シリコーン系コアシェル難燃剤を添加したが、同じ難燃剤を用いた比較例−４に比べて優れた難燃性を示した。
さらに、実施例−７では、縮合リン酸エステル系難燃剤を添加したが、同様に優れた難燃性を示した。
また、実施例−４では、表面に付着させる難燃剤の量を増やして調整したガラス繊維を用いたが、他の実施例同様に優れた難燃性を示した。
以上によって、ガラス繊維の表面処理時に、処理剤に難燃剤を添加することで、燃焼性の改良が認められる。
以上において、特にＵＬ−９４の垂直燃焼試験の評価において、最大燃焼時間は、１０回燃焼の内１回でも１０秒を超えることで、Ｖ−０ＮＧとなるが、比較例のものはＶ−０であっても、最大燃焼時間がＭａｘの１０秒に対して、ゆとりが無く、場合によってはＶ−０ＮＧとなる可能性も高いが、本発明の実施例では、同じＶ−０の場合でも最大燃焼時間が４〜６秒程度であるので、その確率も少なくなるため、安定した高度の難燃性を有していると言える。
尚、曲げ弾性率、及びペレットと成形品の分子量の比較結果から、難燃剤をガラス繊維の表面に付着させることでの影響は認められなった。
Moreover, in Example-5, the flame retardant added separately was changed to the branched dodecylbenzenesulfonic acid potassium salt, but the same flame retardant was used, and the amount of the flame retardant included the equivalent amount of the amount adhered to the glass fiber. Even compared with the added Comparative Example-3, excellent flame retardancy is exhibited.
In Example-6, the silicone-based core-shell flame retardant was added, but the flame retardancy superior to that of Comparative Example-4 using the same flame retardant was exhibited.
Furthermore, in Example-7, although the condensed phosphate ester flame retardant was added, the flame retardance which was excellent similarly was shown.
Moreover, in Example-4, although the glass fiber adjusted by increasing the quantity of the flame retardant made to adhere to the surface was used, the flame retardance which was excellent similarly to another Example was shown.
By the above, the improvement of combustibility is recognized by adding a flame retardant to a processing agent at the time of the surface treatment of glass fiber.
In the above, especially in the evaluation of the vertical combustion test of UL-94, the maximum combustion time becomes V-0NG by exceeding 10 seconds even in one of the 10 combustions, but the comparative example is V-0. However, there is no room for the maximum combustion time of Max of 10 seconds, and there is a high possibility that it will be V-0NG in some cases. However, in the embodiment of the present invention, the maximum combustion time is the maximum even in the case of the same V-0. Since the burning time is about 4 to 6 seconds, the probability is also reduced, so it can be said that it has a high degree of stable flame retardancy.
In addition, the influence by making a flame retardant adhere to the surface of glass fiber was not recognized from the bending elastic modulus and the comparison result of the molecular weight of a pellet and a molded article.
Claims (12)
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| WO2011089915A1 (en) * | 2010-01-22 | 2011-07-28 | 日本板硝子株式会社 | Granular flame-retardant material |
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| JP2000072492A (en) * | 1998-08-27 | 2000-03-07 | Nippon Electric Glass Co Ltd | Glass fiber and glass fiber reinforced thermoplastic resin using the same |
| JP2003277597A (en) * | 2002-03-25 | 2003-10-02 | Teijin Chem Ltd | Glass fiber-reinforced polycarbonate resin composition |
| JP2004043556A (en) * | 2002-07-09 | 2004-02-12 | Asahi Kasei Chemicals Corp | Aromatic polycarbonate type flame-retardant resin composition excellent in residence stability |
| JP2005048072A (en) * | 2003-07-29 | 2005-02-24 | Asahi Kasei Chemicals Corp | Aromatic polycarbonate resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2014590A2 (en) | 2007-07-11 | 2009-01-14 | Ricoh Company, Ltd. | Sheet post-processing apparatus, image forming apparatus, and image forming system |
| WO2011089915A1 (en) * | 2010-01-22 | 2011-07-28 | 日本板硝子株式会社 | Granular flame-retardant material |
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